MEMBRANE PROCESS

PROPERTIES
 MEMBRANE PROPERTIES
Membrane performances depend on the following parameters:
• Physical
– porosity, pore size and pore distribution, thickness,
Tortousity, thermal stability etc.
• Chemical
(a) Surface and electrochemical
– streaming potential, zeta potential (electro-kinetic), surface
charge density etc.
(b) Electrical
– impedance measurements to determine the membrane
conductance and capacitance

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 MEMBRANE PROPERTIES
• Membrane Physical Properties
Some of the more common parameters used to
characterize microporous membranes include the
following:
✓ Pore diameter – range of pore sizes
✓ Porosity – fraction of total membrane volume that is
porous. Typical average porosities from 0.3 to 0.7
✓ Tortousity - length of the average pore compared to
the membrane thickness. Typical range 1.5 to 2.5
✓ Thermal stability – at low T, polymers can be
classified as glassy or crystalline.
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CLASSIFICATION OF MEMBRANE
PROCESSES
1. Gas diffusion in porous solids
2. Liquid permeation or dialysis
3. Gas permeation in a membrane
4. Reverse osmosis
5. Ultrafiltration membrane process
6. Microfiltration membrane process
7. Gel permeation chromatography

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GAS DIFFUSION IN POROUS SOLIDS
▪Gas phase is present on microporous solid
▪The rates of molecular diffusion depend on the pore sizes and the
molecular weights
▪Example of diffusion : molecular, transition, Knudsen

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LIQUID PERMEATION / DIALYSIS

▪concentration differences through a porous membrane drives liquid

phase diffusion
▪Passage of large molecules through the membrane is more difficult
▪This membrane process has been applied in chemical processing
separations such as separation of H2SO4 from nickel and copper
sulfates in aqueous solutions, food processing and artificial kidneys
▪In electrodialysis, separation of ions occurs by imposing an emf
difference across the membrane

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GAS PERMEATION IN A MEMBRANE
▪A polymer type membrane ie rubber, polyamide hence non-porous
solid
▪The solute gas dissolves in the membrane and then diffuses in the
solids to the other gas phase following Fick’s Law
▪Separation of a gas mixtures occurs because each type of molecule
diffuses at a different rate through a membrane
▪Example : membrane separations , helium being separated from
natural gas and nitrogen from air

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REVERSE OSMOSIS
▪A membrane impedes the passage of a low-molecular-weight solute,
placed between a solute-solvent solution and a pure solvent
▪The solvent diffuses into the solution by osmosis
▪Reverse osmosis : reverse pressure difference is imposed which causes
the flow of solvent to reverse, as in desalination of seawater
▪This process is also used to separate other low-molecular weight
solutes ie salts, sugars and simple acids from solvent

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ULTRAFILTRATION MEMBRANE PROCESS

▪Use of pressure to obtain separation of molecules by means of a

semipermeable polymeric membrane
▪Membrane discriminates on the basis of molecular size, shape or
chemical structure
▪Separate relatively high-molecular-weight such as proteins, polymers,
colloidal materials
▪The osmotic pressure is usually negligible because of the high
molecular weights

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MICROFILTRATION MEMBRANE PROCESS
▪Pressure driven flow to separate micron-size
▪Particles larger than ultrafiltration
▪Examples : bacteria, paint, pigment

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GEL PERMEATION CHROMATOGRAPHY
▪Porous gel retards diffusion of high molecular weight solutes
▪Concentration as driving force
▪Useful for analysing complex chemical solutions

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 MEMBRANE PERFORMANCE
Membrane performances are evaluated using the following
parameters:
1. Permeation Flux
▪ Definition: the volume flowing through the membrane
per unit area per unit time. The SI unit used is m3/m2.s
▪ For the case of transport of gases and vapors, the
volume is strongly dependent on pressure and
temperature. As such, gas fluxes are often given in
terms of a "standard condition" which is defined as 0
oC and 1 atmosphere (1.0013 bar).

Membrane
Type
Flux

Pressure 12
 MEMBRANE PERFORMANCE
2. Permeability Coefficient (P) Definition: the transport flux
of material through the membrane per unit driving force per unit
membrane thickness. It's value must be experimentally
determined. The barrer is the commonly used unit for gas
separation and it is defined as:

In general, permeability of a polymer for a gas mixture increases

with decreasing size and increasing solubility (or condensability)
of the gas. The relative permeability of a gas is given below in
order of decreasing gas permeability as:

H2 > He > H2S > CO2 > O2 > Ar > CO > CH4 > N2

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 MEMBRANE PERFORMANCE
3. Permeance (PM)
 Definition: the ratio of the permeability coefficient
(P) to the membrane thickness (L).
 The permeance for a given component diffusing
through a membrane of a given thickness is
analogous to a mass transfer coefficient.

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 MEMBRANE PERFORMANCE
4. Membrane Selectivity ( )
 also known as the permselectivity for one component (A)
over another component (B) is given by the ratio of their
permeabilities:

PA
 AB  [1]
PB

K A DA
 AB 
K B DB [2]

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 MEMBRANE PERFORMANCE
5. Percentage Membrane Rejection (R)
The efficiency of membrane in removing solute
 Cp 
R
1  C 
  100 [4]
 m 
where,
Cp is the concentration solute in permeate
Cm is the concentration of permeate on the membrane
surface
Cm

Cb
Cp

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 TRANSPORT IN MEMBRANES
According to Fick’ Law,

Flux 
Permeabili ty
Driving Force
Membrane thickness
Driving force and permeance is depend largely on the
mechanism of transport

Driving force: pressure gradient, concentration

gradient, electrical force, etc.

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 TRANSPORT IN MEMBRANES
Nature of transport in membrane
a. Bulk flow through pores (membrane is microporous with
pores larger than the mean free path-MFP).

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TRANSPORT IN MEMBRANES
b. Diffusion through pores
(pores are large enough for diffusion, but small
relative to the MFP).

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 TRANSPORT IN MEMBRANES
c. Restricted Diffusion through pores
(if pores are large enough for some species, but not
others).

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 TRANSPORT IN MEMBRANES
d. Solution-Diffusion
(Diffusion through dense membranes with diffusant
dissolved in polymer matrix).

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TRANSPORT: MICROFILTRATION AND
ULTRAFILTRATION
Microfiltration is based on the restricted diffusion of species through
pores: Larger species or particles are restricted from entering pores of
0.1 to 1 micron in size.
Restricted diffusion

Ultrafiltration is similar, except the pore size is even smaller (on the order
of the molecule size) and the number of pores small. This allows for
separation of smaller components, for example separating a small
molecule from solvent.
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 TRANSPORT: REVERSE OSMOSIS
In reverse osmosis a pressure gradient is used to push solvent
through a membrane which is not permeable to the solute. This
pressure must be greater than the osmotic pressure.

Pressure Concentration
Gradient Gradient

The osmotic pressure is required to overcome the driving force to mix,

that is the driving force to move species down their concentration
gradients.

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MEMBRANE PROCESS
Transport Mechanisms
 Transport-Liquid Permeation
Membrane
Small solutes on one liquid phase diffuse
readily because of concentration differences
through a porous membrane to the second
liquid phase (or vapour) phase

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 Transport-Liquid
Permeation Membrane
Concentration profiles for membrane processes: two liquid
films Dense
Permeate
Feed membrane

L
c1 c1i
kc1 c
1iS

kc2
NA c2
c2iS c2i
DAB

c - concentration (kg mol A/m3) 1- bulk fluid

kc - mass transfer coefficient (m/s) 2 - permeate
i - adj to solid iS- in the solid surface
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Series resistances in membrane
processes
• The equilibrium distribution coefficient K’ is
defined as Feed
Dense
membrane Permeate

L
c1 c1i

c c c
K '  
kc1 c1iS
S 1 iS 2 iS
[1]
c c
L
c1i 2i NA
c2iS
kc2
c2
c2i

DAB

• The flux equations through each phase are

equal to each other at steady state and are as
follows
Series resistances in membrane
processes
Flux Equation (Mass Balance)
DAB
N A  kc1 (c1  c1i )  (c1is  c2is )  kc 2 (c2i  c2 ) [2]
L

I II III

Boundary Inside Boundary

layer at the Membrane layer at the
feed side permeate
side

c1is and c2is are unknown and unmeasurable.

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 Substitute c1is = K’ c1i and c2is = K’ c2i into [2]

N A  kc1 (c1  c1i )  PM (c1i  c2i )  kc 2 (c2i  c2 ) [3]

DAB K '
pM  [4]
L
pM - permeance in the solid (m/s)
L - solid thickness, (m)
DAB - diffusivity of A in solid (m2/s)

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 Solving [3] for the concentration difference

NA NA NA
c1  c1i  c1i  c2i  c2i  c2  [5]
kc1 pM kc 2
Adding the equations:
c1  c2
NA 
1 1 1
  [6]
k c1 pM kc 2

NA - flux (kg mol/s m2 )

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Membrane diffusion and liquid film resistance
EXAMPLE 13.2.1
A liquid containing dilute solute A at a concentration
c1 = 3x10-2 kgmol/m3 is flowing rapidly past a membrane of
thickness L = 3.0 x10-5 m. The distribution coefficient
K’ = 1.5 and DAB = 7.0 x 10-11 m2/s in the membrane. The solute
diffuses through the membrane and its concentration on the
other side is c2 = 0.50 x 10-2 kg mol/m3. The mass transfer
coefficient kc1 is large and can be considered as infinite and
kc2 = 2.02 x 10-5 m/s.
a) Derive the equation to calculate the steady state flux NA and
make a sketch.
b) Calculate the flux and the concentrations at the membrane
interfaces.

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 Membrane diffusion and liquid film resistance
Dense
ANSWER : Feed membrane
Permeate

L
c1iS
Kc1=

c1 c1i

kc2
NA c2
c2iS c2i
DAB

Part (a). Since the flow is very rapid, no resistance flow at the feed side of
the membrane. The concentration of C1i= C1. Hence, 1/kCl=0. Equation [6]
becomes,
c1  c2
NA 
1 1 1
 
k c1
0.0
pM kc 2

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 Transport-Liquid
Permeation
Part (b)
D AB K ' 7.0  10 11 (1.5) 6
Calculate pM   5
 3 .5  10 m/s
flux L 3  10
c1  c2 3  10  2  0.5  10  2
NA  
1 / pm  1 / k c 2 1 / 3.5  10 6  1 / 2.02  10 5
 7.458  10 -8 [Link]/s.m 2
 N A  kc2 (c2 i  c2 )  2.02  10 5 (c2 i  0.5  10  2 )

Calculate  c2i  8.692  10 3 [Link]/m 3

concentration, c2 iS c2 iS
 K '  1 .5  
c2is c2 i 8.692  10 3
 c2iS  1.304  10  2 [Link]/m 3

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Exercise:
Question 13.2.1 (a & b)
Question 13.2.2

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 Dialysis Processes
✓ Selectively removing low molecular weight solutes from a solution by
allowing them to diffuse into a region of lower concentration.
✓ Little or no pressure difference: the flux of solute is proportional to
concentration difference.
✓ Solutes of high mw are retained in the feed solution – their diffusivity
is low.
✓ Feed solution - dialyzate (A, B, Solvent, and colloid)
mw A< mw B
A can pass the membrane by concentration gradient.
B cannot or can (with difficulty) pass through the membrane due
to larger molecular size
Transport of A and B is called dialysis.
✓Colloid cannot pass through the membrane
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Liquid Permeation Membrane- Dialysis
Artificial Kidneys
1. To remove waste products (urea, uric acid, NaCl etc)
from blood of persons with kidney disease.
2. Hollow fibre membranes are employed.
3. Blood is pass through the fibre while saline solution is
circulate on the outside.
4. Wastes will diffuse through the membrane to external
solution, while proteins and cells retained in blood.
Removal of salts and sugars from other natural products or other
colloidal solutions.

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 Example 2 : Dialysis Process
Calculate the flux and the rate of removal of urea at steady state
in g/h from blood in a cellophane membrane dialyzer at 37oC. The
membrane is 0.025 mm thick and has an area of 2.0 m2. The mass
transfer coefficient on the blood side is estimated as 1.25 x 10-5
m/s and that on the aqueous side is 3.33 x 10-5 m/s. The
permeance of the membrane is 8.73 x 10-6 m/s. The concentration
of urea in the blood is 0.02 g urea/100 mL and that in the
dialyzing fluid will be assumed as 0.

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 Gas permeation membrane
processes
Series resistances

gas phase solid membrane gas phase

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 Gas permeation membrane
processes
Series resistances

H = equilibrium relation = kg mol/ [Link]

S = solubility = m3(STP)/atm.m3 solid

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 Gas permeation membrane
processes
Series resistances
The flux in each phase :

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 Gas permeation membrane
processes
Series resistances
Permeability :

The flux through the membrane :

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 Types of membranes
For separation of gases

Dense-phase
symmetric
Asymmetric
membrane
membrane

low selectivity & low

permeation fluxes
(relatively thick to avoid tiny Very thin but dense
holes- overcome by Skin on 1 side of
developing silicon polymers Membrane supported
to increase permeability by
by porous substructure
a factors of 10-20.

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 Asymmetric
membranes Floating the mixture film on
microfiltration membrane;
Vertical
alignment of
nanodomains by
using block
copolymer/homo
polymer mixture

Virus with ∼30 nm Preparation of nanopores of

is completely the mixture film by removing
blocked by the homopolymer
nanoporous
membrane, while
proteins with ∼7
nm pass freely
through the pores
in the membrane)

A double-layered nanoporous membrane suitable for virus filtration was developed by researchers
45 at
Pohang University of Science and Technology in South Korea
 Permeability
Effect of temperature (in K):
PM = DABS ln P’A linear function of
1/T & increase of T.
Mixture of gas (T too high would degrade membrane)
A=P’A (The present of water in mixture of gas too
may damage the membrane)
B=P’B

If different
set of unit is
given
Types of equipment for
Gas permeation membrane processes

Flat
membrane

Spiral- Hollow-
wound fiber
membrane membrane
Types of flow (ideal) for
Gas permeation membrane processes
 Model for gas separation
membrane processes
1 5
Complete- mixing
3 Asymmetric
2 4 membrane

Cross flow model

Counter current and

Complete- mixing for
co-current flow
multi component

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Membrane processes

MICROFILTRATION

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 Microfiltration
Dead-end Cross flow

feed
permeate

feed reject

permeate permeate

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 Microfiltration
Dead-end Cross flow (CFMF)

Laboratory batch filtrations Operation similar to reverse

osmosis & ultrafiltration
Membrane replacing filter
paper The bulk solution flow parallel to
the membrane surface not
Particle build up with time as through it
cake – clarified permeate force
through membrane The permeate flow through
membrane carries particles to the
Permeate flux equation surface thus form a thin layer

High flow rate tangential to

P surface sweeps the deposited
Nw  particles toward the filter exit
 ( Rm  Rc ) leaving a relatively thin deposited
cake layer
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Thank You

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